1,6-octadiene derivatives and the preparation thereof

ABSTRACT

A compound represented by the general formula WHEREIN X and Y each represent an electron attracting group and Z represents a hydrogen atom, a mono-valent hydrocarbon radical, a di-valent hydrocarbon radical bonded to X or Y, or an alkadienyl radical represented by the formula -CH2-CH=CHCH2CH2CH2CH=CH2 or alkyl-substituted derivatives thereof, and a process for preparing said compounds by adding a 1,3-diene to an active methylene compound or hydrocarbon-substituted methylene compound having the electron attracting groups X and Y as represented by the general formula X - CH(Z) - Y, wherein X, Y and Z have the same meaning as above, using a palladium compound or a platinum compound as catalyst.

United States Patent Takahashi et a1.

[451 July-11, 1972 1,6-OCTADIENE DERIVATIVES AND THE PREPARATION THEREOF Kuniyuki Takahashi; Go Hata; Akihisa Miyake, all of Kamakura-shi, Japan Assignee: Toray Industries, Inc., Tokyo, Japan Filed: May 27, I968 Appl. No.: 732,108

Inventors:

Foreign Application Priority Data May 26, 1967 Japan ..42/331 14 Aug. 23, 1967 Japan... Dec. 19, 1967 Japan... Jan. 20, 1968 Japan... March 4, 1968 Japan Int. Cl

Field of Search References Cited UNITED STATES PATENTS Bryant et al. ..260/410.9 Hey et al ..260/4l0.9 Hansley et al. ..260/533 FOREIGN PATENTS OR APPLICATIONS 788,302 12/1957 Great Britain OTHER PUBLICATIONS Maehleidt et al., Lower Alkylesters of B-cyclocitrylidenefluoroacetic Acid and B-ionylidenefluoroacetic Acid" Chem Abst. v01. 66 (1967) 55609.

Allen et al., Synthetic Aspects of Free-Radical Addition. 1 Radical Alkylation of Malonic Ester and Related Compounds" Chem Abst. vol. 58 1963) 445b Primary Examiner-Lewis Gotts Assismn! ExaminerCatherine L. Mills Attorney-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A compound represented by the general formula (alkadienyl) XC-Y 1.

wherein X and Y each represent an electron attracting group and Z represents a hydrogen atom, a mono-valent hydrocarbon radical, a di-valent hydrocarbon radical bonded to X or Y, or an alkadienyl radical represented by the formula CH 2CH=CHCH CI-I CH CH=CH2 or alkyl-substituted derivatives thereof, and a process for preparing said compounds by adding a 1,3-diene to an active methylene compound or hydrocarbon-substituted methylene compound having the electron attracting groups X and Y as represented by the general formula X wherein X, Y and Z have the same meaning as above, using a palladium compound or a platinum compound as catalyst.

8 Claims, No Drawings The compounds of this invention are useful as intermediates 5 for preparing surface active agents, lubricants, cosmetic perfumes, and the like and as a comonomer. However, there has been little investigation concerning these types of compounds when Z a hydrogen atom; and the production thereof.

Therefore, the inventors have studied these compounds and X-(lll -Y an" fill-(1H .1), processes for preparing the same and have discovered the X novel and useful compounds together with a process for preparing such compounds economically and effectively. H HHWLHPHI H'F'Lnhulhi'" (V) SUMMARY OF THE INVENTION The aforesaid novel compounds of the present invention 0 may be prepared by reacting a compound represented by the general formula XCII2Y 4CH1=CHCH=CH2 a X Cmz) y, CH-CH=CH-CH CHZCH CH=CH wherein X and Y each represents CHO, COR, CO R", X-CY SO R, CON(R"") CN or N0 where R, R" and R', each represents a monovalent hydrocarbon radical, R" represents a member selected from the group consisting of hydrogen and monovalent hydrocarbon radicals; R may also be a divalent hydrocarbon radical bonded to Z when X or Y is COR; and 2 represents a hydrogen atom, an alkyl radical, a cycloalkyl radical, an aryl radical, or a divalent hydrocarbon radical bonded to X or Y when X or Y is COR; with a 1,3-

l ClI2ClI=CH-CIIzCH1-CH2-CIIC1I:

2. The reaction of internally unsymmetrical l,3-diene compounds, for example, isoprene;

A. When 2 is a hydrocarbon radical;

diene compound represented by the general formula R R R XCH(Z)-Y 2CHz=( JCH=CHz 2 I 3 X (3H CH;

"CZCH Z%CHC=CH-CH CH-CH C=CH wherein R R and R each represents a hydrogen atom or an Y (II) alkyl radical; in the presence of a palladium compound or a platinum compound at a temperature of 0 to 250 C.

DETAILED DESCRIPTION OF THE INVENTION Z a hydwge" 3mm;

There, are no particular limitations as to the hydro-carbon 1= 2 radicals represented by R, R", R, and R"" in the aforesaid X CH3 CH3 definitions but in general there may preferably be employed as HPCHPJI=CH1 the hydrocarbon radicals, allphatlc groups having one-10 car- I bon atoms, alicyclic groups having six-l0 carbon atoms, aro- Y (H) matic groups having six-l0 carbon atoms, and alkylene groups or having two-l0 carbon atoms Also, there are no particular limitations as to the alkyl group, the cycle-alkyl group, the aryl X-ClIr-Y 4CH2=CCH=C1I group and the alkylene group employed and defined in the CIIz-C:CIICI z-CH:CH:-C=OH3 aforesaid general formulas; but there may be preferably used Cm (3H3 an alkyl group having one-eight carbon atoms, a cycloalkyl group having six-eight carbon atoms, and an aryl group having six-eight carbon atoms. Moreover, these hydrocarbon radicals CHI-0:0 H--CI-I -CH CH -C=CH may be substituted with such substituents as halogen and nitro C H CH (nu) groups, and, when X or Y is COR, R may be bonded to Z and 5 a 3 may preferably be combined together to form an alkylene group represented by the formula (CH where n is f bl equal to {W04 g 3. The reaction of terminally unsymmetrical l,3-diene com- Furthermore, there are no particular limitations as to R R Pounds, for elfample, L -P p and R in the aforesaid definitions but in general there may be when z is a hydrocarbon radlcali preferably be employed hydrogen atoms or alkyl radicals having six or less carbon atoms.

In the reaction of this invention, the modes of the addition X Cmz) Y 2CH2 CH CHAJHCH reaction vary with the structures of the 1,3-diene compounds employed and may be classified into three categories: addition ZCCHCI =CH-CHz-CHCIIzCH=CH2= reaction of symmetrical 1,3-diene compounds such as butadiene; that of internally unsymmetrical l,3-diene com (111) pounds such as isoprene; and finally, that of terminally unsymmetrical l,3diene compounds such as l,3-pentadiene. when 2 a hydrogen atom;

al'llhisei three kinds of reaction will be explained schemati- 2OHFCu CH=CHOH3 c y e ow. X

l. The reaction of symmetrical 1,3-diene compounds,for example butadiene; H .llC-CllCIT-Cll:ClI-C1I ?ll(lllzClI:Cllg

A. When Z is a hydrocarbon radical; Y 0 H (ill; (NV) 9045 m I044 003x In the process of this invention, as described above, there are three types of modes of the addition reaction depending on the structure of one of the starting materials, i.e., the 1,3- diene, but the main products in all these reactions are compounds with 2,7-alkadienyl radicals.

As is clear from the aforesaid reaction schemes, by contacting the compound represented by the general formula X CH(Z)Y having a methylene group or a substituted methylene group, said group having at least one hydrogen atom activated by the electron attractive groups represented by X and Y in the aforesaid formula and the 1,3-diene compound defined as above in the presence of a palladium com pound or a platinum compound as catalyst. the above-mentioned addition reaction occurs and the aforesaid novel compound of the present invention can be obtained.

As the starting material employed in the present invention and represented by the formula X CH(Z) Y, there may be employed any compound having at least one hydrogen atom on the carbon atom bonded to the electron attracting group X and Y.

As preferable examples of such compounds, there may be cited a'y-dicarbonyl compounds such as CH COCH COCH o I ll onnooomooom, o0on@,

CzH5C O CHzCOO C211 (151L 00 Cll'gCOO Uglly,

O O 0 H II II and (3H0 CIIzC O O CzH cyano compounds such as NCCH CN, NCCH COOCH NCCH COOC d09, NCCH COC H NCCl-KCH JCOCH NCCH(C H -,COCH NCCH COC l-l NCCH NO CH CON(CH and amide compounds such as H NCO CH CONH and C H HN-COCH CONHC H On the other hand, as the 1,3-diene which is the other starting material for preparing the compounds of this invention, those having only internal double bonds are generally not preferable, but any l,3-dienes having at least one terminal double bond may be employed with no limitation as to the number of carbon atoms. Also, the l,3-dienes may be substituted by groups inactive to the reaction. As such 1,3-dienes, there may be used generally 1,3-butadiene, an alkyl-substituted 1,3-butadiene, and the like, preferably 1,3-butadiene, isoprene, l,3-pentadiene, 1,3-heptadiene, 1,3-octadiene, 1,3- nonadiene, 2,3-dimethylbutadiene, 2,3-diethylbutadiene, 2,3- dibutylbutadiene, and the like.

There is no criticality as to the amount of the l,3-diene relative to the compound represented by the general formula X CH(Z)-Y in the reaction; however, an excessive amount of the l,3-diene is usually used and in particular l-20 mols, preferably 2-6 mols of the l,3-diene is employed per mol of the said co-reactant.

Furthermore, for obtaining the product having four molecules of the l,3-diene as shown in reaction Formula (l")(lll) mentioned above, it is necessary to use more than 4 mols of the 1,3-diene per mol of the compound represented by the formula X-CH Y.

ln order to prepare the novel compound of this invention using the aforesaid two kinds of starting materials, it is necessary to react the two starting materials in the presence of a palladium compound or a platinum compound as catalyst. As yet, the mechanism of the reaction is not completely understood, however, it is theorized that the remarkable action of the catalyst may be caused by the properties of the metal itself in the metal compound as in the cases of various conventionally known reactions using noble metal catalysts. It is to be understood that we do not intend to be bound by this theory. In carrying out the reaction using various compounds of these noble metals as catalysts, it has been found that all of these compounds showed almost the same catalytic actions, some of these experiments being shown below. Therefore, it will be understood that the particular form of the compound of platinum or palladium is not particularly critical in the process of this invention and any platinum compounds and palladium compounds may be employed effectively.

As the palladium catalyst or the platinum catalyst, there may preferably be used salts of these noble metals and complex compounds of these salts with tri-valent phosphorus compounds, arsenic compounds, or antimony compounds. As examples of the palladium compounds, there may be cited inorganic salts, such as PdClg, Pdl PdBr Pd( NQ,) Pd(CNS) Pd(CN and the like; organic salts such as Pd(OCOCH;,)- Pd(OCOCH Cl-I and the like; inorganic complex salts such as H (PdCL,), H (PdCl complex compounds with tri-valent phosphorus and arsenic and antimony complex compounds such as PdCl (PCl PdCl [P(OCH PdCl,[P(C H '2[ (y 6 n)a]2, a)2[ n s)al-2, 2[ fi sh h, 2[ 6 5)3] 2 z[ a 1)3l2 CHaCOPdCII P( 2 5)a]z s 5 2 5)al2, 2[ 2 5)a]z, a l, z 5)al2, a)2 2 5)a]2 6 5)3]-h H H 0-0 0 O CH:

Pd(CO)Cl 2( -2 z)]2, 2( n 5 2)]. PdCl (CH Cl-I-CI-I CH and the like. Also, the preferable examples of the platinum compounds are inorganic and organic salts such as PtBr Ptl PICI Pt(OCOCl-I Pt(OCOCl-l Cl-l and the like; inorganic complex salts such as H PtCl 61-1 0, K Ptl K Pt(CN) 3H O, K PtCl K PtCL, Na PtCI 6H O and the like; complex compounds with tri-valent phosphorus, arsenic and antimony compounds such as [Pt(P(C H ][PtCl [Pl( (Cz s):tl-il 2, P[C|2[AS(C4H9)3]2- PlClz[Sb( 2 n)sl2. (Ci; s)::l1- fi .'|)JllZl- (wherein Py is Moreover, as ammonium salts of palladium or platinum, there may preferably be used (NH [PdCl (Nl-l [PdBr iih hl, LhI kI, UA LL -MA H, and the like. It is to be understood that the foregoing compounds are exemplary only of the materials which may be used as catalysts.

In the process of this invention, the reaction can proceed rapidly, in particular, when phosphine complex salts of palladium or platinum are employed. When a zero-valent palladium or platinum complexes are employed, it is unnecessary to use the preformed complex. A mixture, obtained by reacting a suitable reducing agent with a palladium or platinum salt in the presence of a tri-valent phosphorus or arsenic compound may be used in situ. In this case, sodium hydride, lithium hydride, lithium aluminum hydride, lithiumborohydride, and hydrazine may be used as the reducing agent.

There is no criticality as to the amount of the catalyst used in the process of this invention but the molar ratio of the compound represented by the general formula YCl-I(Z)Y to the palladium or platinum compound is usually in the range of l0-50,000. If the amount of the catalyst is below this range, the activity of the catalyst in the reaction is insufficient. A larger amount of the catalyst than the aforesaid range may be employed but the rate of reaction is in-significantly increased thereby rendering the process unprofitable. The preferable molar ratio of the compound represented by the above general formula to the catalyst is in the range of 50-5,000 when the compound is the 0:,y-dicarbonyl compound and 50-1 ,000 when the compound is one of the other compounds than the dicarbonyl compound.

It is most preferable to conduct the reaction of this invention by adding an alkali metal or a basic alkali metal salt as cocatalyst. As the alkali metal or alkali metal compound used in this case, there are preferably used alkali metals such as lithium, sodium, potassium, rubidium, and cesium; alkali metal hydrides; alkali metal carbonates; alkali metal oxides; and compounds represented by general formulas AOM, MCI-I(CN) and MCH(CN)COOB wherein M represents an alkali metal and A and 8 each represent a hydrocarbon radical, which may be substituted by a group inactive to the reaction, such as, a halogen atom or a nitro group. In the latter case, an aliphatic group having one-four carbon atoms, an alicyclic group having six-l2 carbon atoms may be preferably used although the invention is not limited to these. Moreover, an alkali metal salt of the compound represented by the aforesaid general formula X-CH(Z)-Y, which is one component of the starting materials in this invention may be effecand tively used as the cocatalyst. Therefore, an alkali metal or an alkali metal salt capable of forming an alkali metal salt of the compound of X-CH(Z)Y may be employed.

In particular, when the catalyst is a salt of palladium or platinum or complex compounds of these salts with phosphorus, arsenic, antimony, or nitrogen compounds, it is desirable to use an alkali metal or a basic alkali metal salt together in conjunction therewith.

As the alkali metal compound used in the process of this invention, there may be cited LiH, NaH, KH, RbH, Li O, Na O, K 0, Rb O, Na CO K CO Rb CO C H ONa, C H OLi, C H OK, C H OCs, pC1C,,1-l -ONa, mC1C,,-H,ONa, oCl-C H.,ONa, p-ClC H ONa, mCH;,C H.,OK, o CH C,,H OK, pNO C,,H.,ONa, pC,,H .,-C,,H,,ONa, HO-C,,H,,ONa, CH ONa, C H ONa, C H oRb, C H ONa, CH CHCH,,ONa, n-C.,H OK, tC,,H,,ONa, NaCH(CN)- NaCH(CN)CO C H,,, and the like although the invention shall not be limited to them by any means.

The amount of the alkali metal or the basic alkali metal salt mentioned above is 0.1-100 mols, preferably 1-20 mols per mol of the palladium or platinum catalyst with which it is employed. If the amount thereof is less than 0.1 mol per one mol of the catalyst, the ability of the compound to increase the activity of the catalyst is insufficient while amounts greater than 100 mols is uneconomical since no further enhancement in the catalyst activity is obtained.

The process of this invention can be very easily carried out. For example, the aforesaid catalyst components are mixed in the -,a,'y-dicarb0nyl compound which is one component of the starting materials and then the 1,3-diene is added to the mixture to effect the reaction. In this case, by using a solvent inactive to the reaction, i.e., an aliphatic hydrocarbon, such as hexane, heptane, a cycloaliphatic hydrocarbon such as cyclohexane; an aromatic hydrocarbon, such as benzene, toluene, xylene and the like; or acetone, diethyl ether and the like in an amount equivalent to that of the compound represented by the general formula XCH(Z)-Y, the reaction can be conducted smoothly. Moreover, the post-treatment of the reaction product is facilitated.

Further, when a small proportion ofa phenol is added to the reaction system, the activity of the catalyst is increased and the reaction proceeds rapidly. Accordingly, it is desirable to conduct the reaction by adding 0.1-20 mols of a phenol per mol of the palladium catalyst or the platinum catalyst. If the amount of the phenol is below this range, the ability to increase the activity of the catalyst is insufficient and a larger amount thereof is uneconomical as the activity of the catalyst is not further increased.

As the phenol, there may be preferably used phenol, chlorophenol, dichlorophenol, trichlorophenol, bromophenol, phenylphenol, cresol, xylenol, nitrophenol, hydroquinone, and the like.

The reaction temperature of this invention is generally in the range of 250 C. If the temperature is below this range, the rate of reaction is low, while if temperatures above this range are used byproducts tend to form. Particularly preferable temperatures range between 70 and 160 C.

The alkadienyl compounds which are obtained according to the process of this invention are all new compounds and are useful as a component monomer of various copolymers because of the presence of polymerizable double bonds therein, as a starting material for the production of surface active agents because of the presence of hydrophilic electron attracting substituents together with lipophilic hydrocarbon radicals of relatively long chain (in this case, the alkadienyl group); and furthermore, as a starting material for the production oflubricants and cosmetic perfumes.

Particularly useful products according to the process of this invention are those alkadienyl compounds which are obtainable when symmetrical or internally unsymmetrical dienes are used as 1,3-diene component because of the availability of these dienes and because of their high reactivity.

These compounds may be expressed by the following general formula wherein X and Y are as described heretofore and Z is the same as Z described heretofore or an alkadienyl group of the general formula wherein R, and R are as described heretofore. Particularly preferable among these compounds are those in which R, and R are both hydrogen atoms or those in which R, is a methyl group and R is hydrogen.

The process of this invention and the products according to the process of this invention are described in the following examples. However, it is obvious that the present invention is by no means confined to these examples.

EXAMPLE 1 In a ml. autoclave were charged 19.5 g. (0.15 mol) of ethyl acetoacetate, 0.954 g. (9 m. mols) of sodium phenoxide, and 0.531 g. (3 m. mols of palladium chloride. After replacing the air in the autoclave with a 1,3-butadiene gas, 39 ml. (0.45 mol) of liquefied 1,3-butadiene was added thereto followed by stirring for 1 hour at 100 C. By distilling the reaction product thus obtained under reduced pressure, 28.6 g. of ethyl 2- acety1-4, 9-decadienoate (CH CHCH CH CH CH CHCH CH(COCH )-CO C H having a boiling point of 139 C./5 mm. Hg and m, of 1.4580 and 3.8 g. of ethyl 2- acetyl-2-( 2,7-octadieny1)-4, Q-decadienoate ((CH, CHCH CH CH CH CHC1-1 C(COCH )CO C H having a boiling point of 188 C./5 mm. Hg and "D25 of 1.4759 were obtained. When the same procedure was repeated using 0.612 g. (9 m. mols) of sodium ethoxide instead of sodium phenoxide, 12 g. of ethyl 2-acety1-4, 9-decadienoate was obtained.

EXAMPLE 2 In a 100 ml. autoclave were charged 19.5 g. of ethyl acetoacetate, 2.3 g. (18 m. mols) of p-chlorophenol, and 0.2 G. (9 m. mols) of metallic sodium and after stirring the system for 30 minutes, 0.531 g. (30 m. mols) of palladium chloride and 39 ml. of liquefied 1,3-butadiene were added to the system followed by stirring for 1 hour at C., whereby 28.9 g. of ethyl 2-acetyl-4, 9-decadienoate and 2.9 g. of ethyl 2- acetyl-2-(2,7-octadienyl)-4,9-decadienoate were obtained. When 0.34 g. of metallic potassium was used in lieu of metallic sodium, similar results were obtained.

EXAMPLE 3 In a 100 ml. autoclave were charged 6.5 g. (0.05 mol) ethyl acetoacetate, 0.5 g. of phenol, 0.69 g. of anhydrous potassium carbonate, and 0.18 g. of palladium chloride. After further adding 13 ml. (0.15 mol) of liquefied 1,3-butadiene to the mixture, the system was stirred for 3 hours at 130 C., whereby 7.3 g. of ethyl 2-acetyl-4, 9-decadienoate and 0.9 g. of ethyl 2- acety1-2-(2, 7-octadieny1)-4, 9-decadienoate were obtained. When 0.21 g. of PdC1 (CH CH was used in lieu of palladium chloride, the same results were obtained.

EXAMPLE 4 In 100 m1. autoclave were charged 13 g. of ethyl acetoacetate, 15 ml. of benzene, 0.288 g. (0.25 m. mol) of Pd[P(C,,H.-,);,l, and 26 ml. of liquefied 1.3-butadiene followed by stirring for 30 minutes at 85 C. to provide 4.8 g. of ethyl 2- acety1-4, 9-decadienoate.

When 0.25 g. of phenol was added to the reaction mixture having the same composition as above and the system was reacted under the same conditions as above, 10.8 g. of ethyl 2- acety1-4, 9-decadienoate was obtained.

In a 100 ml. autocalve were charged 13 g. of ethyl acetoacetate, 15 ml. of benzene, 0.007 g. (0.01 m. mol) of PdCl [P(C H and 26 ml. of liquefied 1,3-butadiene followed by stirring for 30 minutes at 85 C. to provide 14.0 g. of ethyl 2-acetyl-4, 9-decadienoate and 13.9 g. of ethyl 2-acetyl- 2-( 2,7-octadienyl)-4, 9-decadienoate.

When the same procedure as above was repeated while using 1 1.6 g. (0.1 mol) of methyl acetoacetate in lieu of ethyl acetoacetate, 15.8 g. of methyl 2-acetyl-4,9-decadienoate (having a boiling point of 111 C./l.5 mm. Hg and n of 1.4588) and 4.9 g. of methyl 2-acetyl-2-(2,7-octadienyl)-4,9- decadienoate were obtained.

EXAMPLE 6 In a 100 ml. autoclave were charged 11.6 g. (0.1 mol) of methyl acetoacetate, 0.108 g. (2 m. mol) of sodium phenoxide, 0.028 g. (0.04 m. mol) of PdCl (P(C H and 43 ml. (0.5 mol) of liquefied 1,3-butadiene followed by stirring for hours at 85 C. to provide 30.2 g. of methyl 2-acetyl-2-(2, 7-octadienyl)-4, 9-decadienoate.

EXAMPLES 7-30 In a 100 ml. autoclave were charged 19.5 g. of ethyl acetoacetate, 1.40 g. of PdCl (P(C l-l and 0.64 g. of sodium phenoxide and thereafter 39 ml. of liquefied 1,3-butadiene was added to the mixture followed by stirring for 1 hour at 1 10 C. to provide 21.0 g. of ethyl 2-acetyl-2-(2,7-0ctadienyl)- 4.9-decadienoate. The same procedure as above was repeated using in lieu of the palladium compound shown above the palladium compounds shown in the following table (Table l and the results obtained are shown in Table 1.

TABLE 1 Palladium Compound (1 mmol) Product ldCl2[ (l1-C4H0)a]z 26. 3 2. 8 l(lClz[Sl)(Cuu5)a]2 18.3 0.8 [l(1(1r-C3lI5) Cl]2 14.3 1.0 ld(1r-C3H )Cl. l(CalI5)3 23. 8 14. 1 ldClz[P(OClIa)a]2 26.1 5.7 PdBrflPUI-Cfliohlz 18. (i 20. l Pd(NO3)2[P(C51'I5 a]z 17. 3 22. 3 Pd(CNS)z[P (0 1103]: 19. 8 19. G PdBl'2 29. 7 3. 1 PdIz 29. 0 3. 0 Pd(NO3)2 28.3 2. 4 Pd(OCOCH )2 29.3 4.1 H2[Pd 1 21. 3 3.1 HdPdClu] 23. 1 3. 8 Pd(CN)z 19.1 1. 0 P(1(CNS)2 27. 9 4. 3 Pd(CO)Clz 21.3 2.4 PbBrz[P(CzH5)3]2 18. 3 23. .l PdBIz[P(Oy0lOCaHu)3]2 22. 1 20. 9 .PdBr1[Sb(O3H-1)I2 28. 4 8. 6 27. [PdClz(CH2=C 2)]: 14. 3 0. 8

28 l'dClz 16. 4 l. 0

29 Pd(AcAc)z 22. 9 20. 1 30 CH3PGBI[P(C2H5)3]2 28. 6 17. 9

*Pd(ACAG)z PdOZI) acetylacetonate.

EXAMPLE 31 In a 100 ml. autoclave were charged 14.0 g. of 2-acetyl cyclohexanone, 0.318 g. of sodium phenoxide, and 0.35 g. of PdCl [P(CH The system was stirred for 2 hours at 90 C. to provide 16.3 g. of 2-acetyl-2-(2,7-octadienyl)-cyclohexanone(having a boiling point of 149 C./3.5 mm. Hg and n of 1,4759 1,4759

When the same procedure was repeated while using 0.288 g. of Pd]P(C H instead of the above palladium compound, 13.4 g. of 2-acetyl-2-(2, 7-octadienyl) cyclohexanone was obtained.

EXAMPLE 32 The same procedure as in Example 6 was repeated while using 20.4 g. (0.3 mol) of isoprene in lieu of 1,3-butadiene to provide 27.6 g. of ethyl 2-acetyl-4,9-dimethyl-4,9- decadienoate (having a boiling point of l03l04 C./0.05 mm. Hg and n,,"" of 1.4629.

EXAMPLE 33 In a 100 ml. autoclave were charged 24.0 g. (0.15 mol) of diethyl malonate and 0.425 g. of a complex of triphenyl phosphine and After further adding 39 ml. of liquefied 1,3-butadiene. the system was stirred for 1 hour at 100 C. to provide 24.8 g. of diethyl 2,7-octadienyl malonate (having a boiling point of l34-l35 C./3 mm. Hg and m, of 1.4496) and 4.3 g. of diethyl bis( 2,7-octadieny1)malonate (having a boiling point of l84l 88 C./3 mm. Hg and n of 1.4672).

When the same procedure as above was repeated while using 13.2 g. (0.1 mol) of dimethyl malonate in lieu of diethyl malonate there was produced 15.8 g. of dimethyl 2,7-octadienyl malonate (having a boiling point of 1 17 C./ 1 mm. Hg and n,, of 1.4563) and 2.5 g. of dimethyl bis(2,7-octadienyl)malonate (having a boiling point of 178 C./1 mm. Hg and n of 1.4735).

EXAMPLE 34 In a 100 ml. autoclave were charged 13 g. (0.1 mol) of ethyl acetoacetate, 0.18 g. (0.25 m. mol) of PdCl (Ph P) 0.29 g. (2.5 m. mols) of sodium phenoxide, 22.4 g. (0.33 mol) of isoprene, and 15 ml. of benzene. The mixture was stirred for 20 hours at C. to provide 22.6 g. of ethyl 2-acetyl-4,9- dimethyl-4,Q-decadiehoate and 4.8 g. of ethyl 2-acetyl-2-( 2,7- dimethyl-2,7-octadienyl)-4.9-dimethyl-4,9-decadienoate (having a boiling point of 160l 62 C./0.01 mm. Hg and n of 1.4910).

EXAMPLE 35 The same procedure as in Example 34 was repeated while using 22.4 g. of 1,3-pentadiene percent in purity) instead of isoprene to provide 8.5 g. of ethyl 2-acetyl-3,7-dimethyl-4,9 -decadienoate (having a boiling point of 104-l05 C./0.35 mm. Hg and m? of 1.4569.

EXAMPLE 36 The same procedure as in Example 34 was repeated while using 24.6 g. (0.3 mol) of 2,3-dimethyl butadiene instead of isoprene to provide 3.8 g. of ethyl 2-acetyl-4,5,8,9- tetramethyl-4,9-decadienoate (having a boiling point of 122 C./3 mm. Hg and 11,, of 1.4700).

EXAMPLE 37 The same procedure as in Example 34 was repeated while using 10.0 (0.1 mol) of acetylacetone in lieu of ethyl acetoacetate to provide 15.8 g. of 3-(2,7-dimethyl-2,7-octadienyl)-2,4-pentanedione (having a boiling point of 9698 C./0.02 mm. Hg and n of 1.4808) and 9.0 g. of 3,3-bis(2,7- dimethyl-2,7-octadienyl)-2,4-pentanedione (having a boiling point of l50l 52 C./l0"'* mm. Hg and m, of 1.4910).

EXAMPLE 38 In a 500 ml. autoclave were charged 72 g. of ethyl malonate, 0.4 g. of sodium, 3.0 g. of phenol, 0.93 g. of triphenyl phosphite, 0.354 g. of palladium chloride and 172 ml. of liquefied butadiene and the system was stirred for 10 hours at 90 C. to provide g. of diethyl bis(2,7-octadienyl) malonate.

In a 100 ml. autoclave were charged 15.0 g. (0.15 mol) of acetylacetone, 1.1 g. of sodium salt of acetylacetone, 0.35 g. of PdCl [P(C H and 39 ml. of liquefied butadiene. Thereafter, the mixture was stirred for 3 hours at 130 C. to provide 13.1 g. of 3-(2,7-octadienyl)-2,4-pentanedione (having a boiling point of 136 C./7 mm. Hg and n of 1.4800) and 3.8 g. pf 3,3-bis(2,7-octadienyl)2,4-pentanedione (having a boiling point of 171 C./3 mm. Hg and m of 1.4837.

Further, in a 100 ml. autoclave were charged 4.0 g. (0.036 mol) of 1,3-cyclohexanedione, 0.104 g. (2 m. mols) of sodium methoxide, 0.140 g. (0.2 m. mol) of PdCl Ph P) and 10 ml. of liquefied butadiene, and then the mixture was stirred for 1 hour at 85 C. to provide 3.6 g. of 2,2-bis(2,7-octadienyl)- l ,3- cyclohexanedione (having a boiling point of 13814 1 C./10 3 mm. Hg).

EXAMPLE 40 In a 100 ml. autoclave were charged 15.6 g. (0.1 mol) of 2- ethoxycarbonylcyclopentanone, 0.64 g. (6 m. mols) of sodium phenoxide, 1.40 g. (2 m. mols) of PdCl [P(C H and 26 ml. of liquefied butadiene. The system was stirred for 2 hours at 100 C. to provide 15.8 g. of 2-(2,7-octadienyl)-2-ethoxycarbonylcyclopentanone (having a boiling point of 140 C./2 mm. Hg and ru of 1.4739).

The above procedure was further repeated while using 13.6 g. of isoprene in lieu ofliquefied butadiene to provide 25.4 g. of 2-ethoxycarbonyl-2-( 2,7-dimethyl-2,7-octadienyl cyclopentanone (having a boiling point of l38140 C./0.6 mm. Hg and n,, of 1.4791).

EXAMPLES 41-47 In a 100 ml. autoclave were charged 13.0 g. of ethyl acetoacetate, ml. of benzene, 0.25 m. mol ofa palladium complex shown in Table 2 below, and 26 m1. of liquefied butadiene. The mixture was then stirred for 1 hour at 95 C. The

results are shown in Table 2.

TABLE 2 Example Palladium complex (0.25 mmole) 41 [(COII50)3P%1Pd 10.5 4L [(p-Cl-Cal'h 3P]4P(l 13.0 13. J 43 e s lp-Clh-Callqhlhld 17. 1 4.3 14 [(CsllslaP]; Pd 14.8 6.1 45 [(CulIQsAShPd 8.0 2.1

413 i lICCOOCIIg 11.0 11.7

l s)a]2 ll HC C O 0 C113 47 Hfi-CO 12.0 7.1

l o s)al2 0 H C-CO CO CH:

CH2:CIIC1'I2CH2CH2CI :CHCH2CI COZCZHS b ([30 CH3 (CHz=CHCHzCH2CHzCH=CHCH2)2--C-C 0202115 EXAMPLE 48 In a 100 ml. autoclave were charged 15 ml. ofbenzene, 13.0 g. of ethyl acetoacetate, 0.318 g. of sodium phenoxide, 0.288 g. of Pd[P(C H and 26 ml. of liquefied butadiene. The mixture was then heated for 30 minutes to 85 C. to provide 10.5 g. of ethyl 2-acetyl-4,9-decadienoate. Further, when the same procedure was repeated without the addition of sodium phenoxide, 4.8 g. of ethyl 2-acetyl-4,9-decadienoate was obtained.

EXAMPLE 49 In a 100 ml. autoclave were charged 15 m1. of ethyl ether, 0.177 g. of palladium chloride, and 1.048 g. of triphenyl phosphine. After adding to the system 0.038 g. oflithium aliminum hydride, the system was stirred for 30 minutes. Thereafter, 13.0 g. of ethyl acetoacetate and 26 m1. of liquefied 1,3-butadiene were added to the system and the resulting mixture was stirred for 30 minutes at 100 C. to provide 13.5 g. of ethyl Z-acetyl-4,9-decadienoate and 9.8 g. of ethyl 2-acety1-2-( 2,7- octadienyl)-4,9-decadienoate. When 0.1 15 g. of sodium hydride or 0.063 g. of lithium borohydride was used in lieu of lithium aluminum hydride, similar results were obtained.

EXAMPLE 50 In a 100 ml. autoclave were charged 20 ml. of ethyl ether, 0.177 g. of palladium chloride, and 0.406 g. of tributyl phos phine. After the addition of 0.063 g. of lithium borohydride, the system was stirred for 30 minutes. Further, 15.0 g. of acctylacctonc was added and the resulting mixture was stirred for 1 hour at C. to provide 15.2 g. of 3-(2,7-octadicnyl)- 2,4-pentancdionc and 12.6 g. of 3,3-bis (2,7-octadicnyl)-2,4 pentanedione.

EXAMPLE 51 In a ml. autoclave were charged 13 g. (0.1 mol) of ethyl acetoacetate, 0.62 g. (0.5 m. mol) of tetrakistriphenylphosphine platinum (Pt P(C H and 15 m1. of benzene. After replacing the air in the autoclave with 1,3-butadiene gas, 26 ml. (0.3 mol) of liquefied 1,3-butadiene was added to the system and the mixture was stirred for 8 hours at 85 C. After removing unreacted materials and benzene from the product by distillation, the residue was distilled under reduced pressure to provide 12.3 g. of ethyl 2-acetyl-4,9-decadienoate (CH CH(CH CH CHCH CH(COCH -,)COOC H,,) and 3.9 g. of ethyl 2-acetyl-3-vinyl-7-octenoate (CH CH(CH CH(CH CH )CH (COCH )COOC H and 17.8 g of ethyl-2-acetyl-2- (2,7-octadieny1)-4, 9-decadienoate ((CH CH(CH );,CH CHCH C(COCH COOC H EXAMPLES 52-69 The same procedure as in Example 51 was repeated using various platinum complexes shown in the following table, the results of which are shown in Table 3.

TABLE 3 Ex. Catalyst XCH(Z)Y g(m mole) g (m 52 Pt[P(C H C H ONa CH COCH ,COOC H 0.62 g (0.5 m mole) 0.48 g (7 mmol) 13g (0.1

mol 53 picl mc up C H -,ONa CH COCH COOC H 0.40 (0.5) 0.81 (7) 13 (0.1) 54 PtC1 [P(C.,H Pcl-C,,H OH, Na CH COCH C OOC,H 0.40 (0.5),2.3(18), 0.2(9) 13(0.1) Ex. Catalyst XCH(Z)Y g(m mol) g(mol.) 55 PtCl l P( 00 1-1 1,, c moua cn cocn COOC,H 0.42(0.5) 0.81(7) l3(0.1) 56 Pt[P(OC H C H oNa CH COCH cooc u, 0.65 (0.5), 081(7) 13 (0.1) 57 umcusmo, c,,H,oNa crncocu COOC H, 0.41(0.8) 1.l6(10) 13(0.1) K PtCl C,,H,,ONa C H COCH COOC H 0.32(1) 1.l6(10) 13(0.l) 59 Pt(OCOCH C H oNa CH COCH COOC,H,, O.31(l), 1.l6(10) l3(0.1) 60 PtCl [P(C H C.,H -,ONa CH,,COCH

11 COCH 0.40(0.5), 0.131(7) 10(0.1) 61 PtC1-,IP(C.,H ],,t-C,H OK CH,,COCH

COCH; 0.40 (0.5) 0.8(7) 10(0.1) 62 Pt{P(C H,,) C,,H,,ONa CH COCH,

COCH 0.62 (0.5) 081(7) 10(0.1) 63 PTCl [P(OC H,,) C H ONa CH COCH COCH 0.42 (0.5), 0.81 (7) 10 (0.1) 64 .l= 5 5) Na CHQ(COOC2HS)2 0.40 (0.5), 081(7) 16(0.1) 65 Pt[P(OC,,H,) C H ONa CH (COOC H 0.65 (0.5) 0.81 (7) 16 (0.1) 66 PtC12IP(CnH5)3]z CQH5ON8 (I? QCOOCzH 67 Pt[P(C5H5)3]4 CrH ONa R TCOOCZHI' 68 Pt[P( uHr)a14 f l-COOCzHs 60 PtCl{As(CuH)a]z 0,3501% TABLE 3 Ex. Reaction time Product (g) hr A B C 52 5 4.3 g g 15.8 g 53 5 3.9 3.8 21.7 54 8 8.3 19.5 55 8 4.9 19.2 56 8 6.2 15.7 57 13.9 58 10 12.3 59 10 7.3 60 8 3.2 2.6 17.2 61 8 5.2 1.2 16.8 62 10 1 1.3 63 10.8 64 5 20.3 5.2 65 5 15.3 4.1 66 5 24.6 g 67 5 21.0 68 5 10.8 69 10 22.8

Reaction conditions: 26 ml (0.3 mol) of liquefied 1,3-butadiene 15 ml of benzene Reaction temperature: 120C in Example 56 130C in Examples 59. 60 and 61, and 85 C in other examples.

In a 100 ml. autoclave were charged 13 g. (0.1 mol) of ethyl acetoacetate, 0.42 g. (0.5 m. mol) of PtCl, P(C H 0.81 g.

(7 m. mols) of sodium phenoxide, 15 m1. of benzene, and 20.4

g. (0.3 mol) of isoprene. The system was reacted for 130 C. at 10 hours to provide 19.3 g. of ethyl 2-acetyl-4,9-dimethyl-4,9- decadienoate (Cl-l C(CH )(C1-1 CH C(CH )CH CH(COCH )COOC H and 5.8 g. of ethyl 2-acetyl-2-(2,7- dimethyl-2,7-octadienyl)-4,9-dimethyl-4.9-decadienoate (CH2 5)( 2).1 n) 2)2 (COCH )COOC H EXAMPLE 71 In a 100 ml. autoclave were charged 0.12 g. (0.5 m. mol) of Pd(NH no 0.58 g. (5 m. mols) OF C H oNa, 13 g. (0.1 mol) of CH COCH COOC H and 26 ml. ofliquefied 1,3-butadiene followed by stirring for 2 hours at C. After removing unreacted materials by distillation, the residual product was distilled under reduced pressure to provide 16.5 g. of CH COCH(COOC H,',)CH CH CH(CH2).-.CH CH and 7.4 g. of CH COC(COOC H )(CH CH Cl-1(CH CH CH EXAMPLES 72-90 The same procedure as in Example 71 was repeated while using 0.5 m. mol of a palladium complex shown in the following table instead of Pd(NH N0 the results of which are shown in Table 4.

TABLE 4 Ex. Palladium CH;,COCH CH COC No. Complex (COOC H (COOC H CH CH(CHz)a (CHQCH C1'1(CH 2)3 CH 2 AS) CH 2MB) 72 trans-l Pd (NI-19 Gb] 19.4 1.8 73 aLl (Cl,H O 17.8 2.9 74 [Pd (Pyhcl l 16.4 1.4 75 [Pd (en) C1 15.0 0.5 76 1 :|)41

'[PdCL] 18.7 2.3 77 trans-[Pd (NH Br,] 19.8 2.4 78 [Pd(Py) 1,] 15.3 3.9 79 [Pd( en) C1 13.4 0.3 80 [Pd(en),1 13.9 0.5 81 {Pd(dpy)C1- 10.3 0.2 82 [Pd(NH (C 001 1 1.3 0.7 83 [Pd(dpy) (CNS)21 9.1 84 [Pd(CH NH NH) Br]; 16.3 2.7 86 [Pd(C H .,Nl-1

C1 15.4 1.2 87 [Pd(C l-1 ,NH)

C1,] 16.7 2.9 88 Pd(Cl'1 C(NO1-1) (NOH)CH3)2 9.3 89 (N11 PdCl 18.3 2.8 90 (NH )2PdB1' 18.1 3.2

EXAMPLE 91 In a m1. autoclave were charged 0.12 g. (0.5 m. mol) of Pd(N H:s)2NOz)2. 0.58 g. (5 m. mols) of C.;H -,ONa 10 g. (0.1 mol) of CH COCH COCH and 26 ml. of liquefied 1,3-butadiene followed by stirring for 5 hours at l20-l 30 C. After removing unreacted materials by distillation, the residual product was distilled under reduced pressure to provide 10.8 g. of (CH CO) CHCH CH CH-(CH-Q G1 CH and 2.3 g. of (C1-l -,C0) C(CH CH'= Cl-l(C1-l CH CH EXAMPLE 92 In a 100 ml. autoclave were charged 0.106 g. (0.5 m. mol) of trans-[Pd(Nl-1 Cl 0.58 g. (5 m. mols) of C H ONa, 16 g. (0.1 mol) of CH (COOC H and 26 ml. (0.3 mol) of liquefied 1,3-butadiene followed by stirring for 2 hours at 85 C. After removing unreacted materials, the residue was subjected to a distillation under reduced pressure to provide 16.9 g. of (COOC H C1-1CH Cl-1 Cl-1(Cl-1 CH CH and 3.1 g. of(COOC 1-1 C(CH Cl-1 CH(CH CH CH EXAMPLES 93-102 The same procedure as in Example 92 was repeated while employing in lieu of C H ONa 0.5 m. atom of the alkali metal or 0.5 m. mol of the basic alkali metal salt as shown in the following table, the results of which are shown in Table 5.

TABLE 5 EX. Alkali metal or cooc.11. ,c11 (cooc uo qcu,

No. basic 811m CHZCH 011C11 CH c11 c11, metal salt CH CHAg) CH CH,),(g)

95 NaH 16.3

I00 c..H.-.oLi 15.3

NHCH(CN) L] 1 2 COzCz r, 14.8 [3

C1=H.'.OCs 13.7

EXAMPLE 103 In a 100 ml. autoclave were charged 0.16 g. (0.5 m. mol) of [Pt(NH )B4]C,, 0.58 g. (5 m. mols) of C H ONa, 11.4 g. (0. mol) of CH COCH COOCH and 26 ml. (0.3 mol) of 1,3-butadiene followed by stirring for 20 hours at l32-l40 C. After removing unreacted materials by distillation, the residue was distilled under reduced pressure to provide 10.2 g. of CH COCH(COOCH )CH CH CH(CHQ CH CH and 1.1 g. of(CH CO)C(COOCH )(CH CH CH(CH CH CH EXAMPLES 104-114 The same procedure as in Example 103 was repeated while using 0.5 m. mol of each of the platinum complexes shown in the following table in lieu of [Pt(NH ]C the results of which are shown in Table 6.

EXAMPLE 1 In a 100 ml. autoclave were charged 0.12 g. (0.5 m. mol) of Pd(NHhd 3) (NO 0.58 g. (5 m. mols) of C H ONa, and 13 g. (0.1 mol) of CH COCl-l COOC H and the air in the autoclave was replaced with an arogon gas. Thereafter, 20.4 g. (0.3 mol) of isoprene was added to the system and the system was stirred for 10 hours at 120l30 C. After removing unreacted materials from the reaction product, the residue was distilled under reduced pressure to provide 10.2 g. of

EXAMPLE 1 16 The same procedure as in Example 1 15 was repeated while employign 20.4 g. of 1,3-pentadiene instead of isoprene to provide 7.3 g. of (CH;,CO)CH(COOC H,,)CH(CH;,)CH CHCHCH(CH;,)CH CH CH EXAMPLE 1 17 The same procedure was repeated as in Example 1 15 while using 24.6 g. o1 2,3-dimelhylhutadiene in lieu of isoprene to provide 23 g. of ((H CO)CH(COOC,H )CH C((H;,) C((H )CH CH (H((H;,)C(CH1) CH.

EXAMPLE 118 In a 100 ml. autoclave were charged 0.28 g. (1 m mol)- of (NHQ bPdCLJ, 11.6 g. (10 m. mols) ofC H ONa, and 11.4 g. (0.1 mol) of CH:,CH(COCH;,) and the air in the autoclave was replaced with a 1,3-butadiene gas. Then. 26 ml. (0.3 mol) of liquefied 1,3-butadiene was added to the system followed by stirring for 10 hours at 120l30 C. After removing unreacted materials from the reaction product, the residue was distilled under reduced pressure to provide 13.1 g. of (CH CO) C(CH )CH --CH CH(CH CH CH (having a boiling point of 132133 C.) /4 mm. Hg.

EXAMPLE 1 19 In a 100 ml. autoclave were charge 6.3 g. (0.05 mol) of aformylcyclohexanone, 0.1 15 g. (0.1 m. mol) of Pd[P(C H 10 ml. of benzene, and 13 ml. liquefied butadiene followed by stirring for 1 hour at C. The reaction liquid thus obtained was distilled under reduced pressure to provide 9.8 g. of u-(2,7-octadienyl)-a-formylcyclohexanone (having a boiling point of 158 C./45 mm. Hg. n of 1.4880). The product was confirmed by elementary analysis infrared absorption spectra and NMR spectra. The amount of high boiling residues was 0.6 g.

EXAMPLE 120 In a ml. autoclave were charged 25.2 g. (0.2 mol) of aformylcyclohexanone, 0.070 g. (0.1 m. mol) of PdCl [P(C H a[ 0.218 g. (2 m. mols) of sodium phenoxide and 51 ml. (ca. 0.6 mol) of liquefied butadiene followed by stirring for 40 minutes at 85 C. to provide 40.8 g. of a-(2,7-octadienyl)-aformylcyclohexanone. The amount of high boiling residues was 2.9 g. The same procedure as above was repeated while using 40.8 g. of isoprene instead of butadiene to provide 21.3 g. of 01-2,7-dimethyl-2,7-octadienyl)-a-formy1cyclohexanone.

EXAMPLE 121 ln a 100 ml. autoclave were charged 10.0 g. (0.1 mol) of 3- formyl-2-butanone, 0.053 g. (0.1 m. mol) of Pdl [P(C l-l 0.122 g. (l m. mol) of potassium phenoxide, and 26 m1. of liquefied 1,3-butadiene followed by stirring for 1 hour at 85 C. to provide 5.5 g. of 3-(2,7-octadienyl)-3-formyl-2-butanone (having a boiling point of 121 C./4.5 mm. Hg. n of 1.4672). The amount of high boiling residues was 0.4 g.

EXAMPLE 122 In a 100 m1. autoclave were charged 18.2 g. (0.1 mol) of aformylcyclododecanone, 0.070 g. (0.1 m. mol) of PdCl [P(C H a[ 0.054 g. (1 m. mol) of sodium methoxide and 26 ml. of liquefied 1,3-butadiene followed by stirring for 1 hour at 85 C. to provide 26.1 g. of a-(2,7-octadienyl)-a-formylcyclododecanone.

EXAMPLE 123 In a 100 ml. autoclave were charged 6.5 g. (0.05 mol) of ethyl a-formylpropionate, 0.035 g. (0.05 m. mol) of Huwnmnz- 4.1-; 5.4 PdCl [P(Cl-I 0.054 g. 1 m. mol) of sodium methoxide and 13 ml. of liquefied 1,3-butadiene followed by stirring for 1% hours at 85 C. to provide 7.0 g. of ethyl a-(2,7-octadienyl)-a-formylpropionate (having a boiling point of 119 C. 5 /3.5 mm. Hg, n,, of 1.4551). The amount of high boiling 1| residues was 0.9 g. The same procedure as above was repeated 0 while using butyl a-formylpropionate instead of ethyl a-for- 141 Pt[P(CH ]2- CH-COOMe 4.8 5.4 mylpropionate to provide butyl a-(2,7-octadienyl)-a-formyl- OH COOMG proplonate' 42 H01 0 H )P(C H) 1 1r- EXAMPLE 124 22 tgialaf g 5 3 3.2 In a 100 ml. autoclave were charged 19.2 g. ethyl -for- 1:1: ptc l zgocifi hh 2: Q12 mylphenylacetate, 0.62 g. of Pd[P(C 5)3]4, 10 of l H benzene and 26 ml. of liquefied 1,3-butadiene followed by 15 2 stirring for 1 hour at 100 C. to provide 23.1 g. of ethyl a-( 2,7- octadienyl)-a-formylphenyl-acetate (having a boiling point of EXAMPLE 146 j amount of hlgh boil In a 100 ml. autoclave were charged 5.7 g. (0.05 mol) of mg resldue was ethyl cyanoacetate (NC-CH COOC H5). 0.12 gof EXAMPLE 125 Pd[P(C H 0.l2 g. (1 m. mol) of sodium phenoxide, 15 In a 100 ml. autoclave were charged 19.2 g. (0.1 mol) of of benzene and 13 (015 mol) of liquefied ethyl formylphenylacetate, 0212 (2 mol) of Sodium tadiene followed by stirring for 2 hours at 85 C. After removphenoxide, g m l f PdCl2[P(CH5)3]2 and 2 111g. unreacted materials and benzene by diSllllZlllOl'l, the ml. of liquefied 1,3 butadiene followed by stirring for 10 resldue was dlstllled under reduced pressure to provide 5.2 g. o of ethyl 2'cyan-4,9-decadienoate [(CH CH(CH CH minutes at 85 C. to provide 26.9 g. of ethyl a-(2,7-octadlenyl)-a-formylphenylacetate. The amount of high boilin CHCH2CH(CN)COOC2H5 (havmg a bolmg pomt of residue was 1 5 g g l20-l20.5C./ 2 mm. Hg. n of 1.4553), 1.8 g. of ethyl 2- cyan-3-vinyl-7-octenate (CH CH(CH -,CH(CH EXAMPLE 126 CH )CH(CN)COOC H (having a boiling point of from In a 100 ml. autoclave were charged 6.6 g. (0.1 mol) of ll5-l16 C./ 2 mm. Hg. n of 1.4535), and 8.9 g. ofethyl 2- malononitrile (NCCH CN), 0.35 g. (0.5 m. mol) of cyan-2-( 2,7-octadienyl)-4,9-decadienoate (having a boiling dichlorobis(triphenylphosphine) palladium (PdCl [P(C 1-I poin of l ll 2 C-/ 2 mm- Hg. n of 1.4747). 0.58 g. (5 m. mols) of sodium phenoxide, 15 ml. of benzene g and 26 ml. (0.3 mol) of liquefied 1,3-butadiene followed by 5 EXAMPLE 147 Stirring for 2 hours at After remfwing 'f l mated In a 100 ml. autoclave were charged 11.3 g. (0.1 mol) of als and benzene by distillation, the residue was distilled under ethyl cyanoacetae, 1 015 l) f PdCl [P( C l-1 h] reduced 1P to Provlde of z7octadlenyl' 0.29 g. (2.5 m. mol) of sodium phenoxide, 15 ml. of benzene malononitfile 2 2 :1 CHCHZ'CH(CN)2) and 26 ml. (0.3 mol) of liquefied 1,3-butadiene followed by g a boiling P 0f -vflq P 14626) 4 stirring for 1 hour at 85 C. to provide 5.0 g. of ethyl 2-cyanand of QJ- Y l": 2 4,9-decadienoate, 1.2 g. of ethyl 2-cyan-3-vinyl-7-octenate 2)a 2)2 )2] g a bollmg I of and 19.8 g. of ethyl 2-cyan-2-(2, 7-octadienyl)-4,9- from 174 10 176 4 mm. Hg, "D25 Of decadienoa[e EXAMPLES 127445 EXAMPLES 148-156 The same procedure as in Example 126 was repeated while v using various palladium or platinum compounds, shown in the The 531116 Pmcedul'e as above was repeated while g Y following table instead of pdclzlpuj 61493] 2, the results f ous alkali metal salts (2.5 mol) under the same conditions which are Shownin Table as in Example 147 only instead of sodium phenoxide, the TABLE 7 results of which are shown in Table 8.

Products (g.) TABLE 8 Example N o. Palladium or platinum compounds Products 127 PdC1z[P(OCaH5)Bl2 1.6 10.5 Example No. Alkali metal salts 12s... PdClz 5.8 3.2 129. PdCl2[PO1-3]2 3. 4 8. 2 NaH 3. 2 0. 2 13. 4 130. PdCl2[AS(CoH5)3l2 2. 1 9. 6 P-Cl-CaH4ONfl 4. 3 l. 8 20. 3 P-NOzCaH4OK 8.2 0.4. 13.2 131 Pd[P (CtHOilfl 0 2.9 9.7 NazCOa 7.3 1.1 15.4 H 152 PC6H5'-CflHr0Na 3.5 2.4 18.2 153 CoHsOLI 1.8 0.4 10.3 154-. C2H5OR1J 4.2 0.1 5.8 155 CH2=CHCH2ONa 9.3 1.1 11.2 156 NaCH(CN)COzCzH 5.8 3.2 19. 1

NC-CHF-COQCzHs O CH2CH=CHCH2CH2CH2CH=CH2 132 Pd[P (011E031: CH .-COOM0 3.4 1 NC --CH-C0OC2H5 CHCOOMe CH2=CHCHCH2CH2OH2CH=CH2 133 M a (OH2=CHCH2CH2OH2CH=CHCH1 2C(CN)COOCzH *fi EXAMPLE 157 In a ml. autoclave were charged 5.7 g. (0.05 mol) of 3%: gggf fifli 3:2 2 ethyl cyanoacetate, 0.20 g. (0.25 mol) of dichlorobis( triphen- 136 PdClz( n=-CH-CH=CH2) 1.8 3 ylphosphine)platinum (PtCl [P(C H 0.18 g. (2.5 m. g; fifgfgg fg mols) of sodium phenoxide, 15 ml. of benzene and 13 ml. 6.2 2.8 75 (0.15 mol) of liquefied 1,3-butadiene followed by stirring at nag-n IOIMA 85 C. for 15 hours to provide 2.3 g. of ethyl 2-cyan-4, 9- decadienoate and 4.2 g. of ethyl 2-cyan-2-(2,7-octadienyl)- 4,9-decadienoate.

EXAMPLES 158-168 The reaction of 1,3-butadiene and active hydrogen compounds shown in the following table was conducted by the same procedure as in Example 157 using the catalyst shown in the table, the results of which are also shown therein.

TABLE 9 Lique- Ex. Catalysts X CH(Z) Y fied l,3- No. g(mol) g(mol) butadiene ml.(mol) 158 Pd[P(C,,H ],,C H,ONa CH CH(CN)COCH ml. 0.29g(0.25mmol), 0.29g 3.8g(0.038mol) (0.l2) (2.5mmols). 159 PdCl [P(C,,H,,) ],C, H ONa NCCH CONH 9 0.18(0.25),O.29(2.5) 4.2 (0.05) (0.1) 160 PdC1 [P(C,,H C H ONa C H,,COCH CN 9 0.l8(0.25),0.29(2.5) 7.3(0.05) (0.1) 161 PdCl [P(C,,H C H ONa NCCH(p CH C,,H ,)COCH 13 0.18(0.25)0.29(2.5) 8.7(0.05) (0.15) 162 Pd[P(C H,,) CH ONa NCCH(C,,H 13

COC .,H 0.29(O.25),0.54(10) 12.2 (0.25) (0.15) 163. PdCl:[P(C@H )3] CoH oNa O 13 0.l8(0.25), 0.29(5) 0.15

164 PdCl [P(C H CHONa C,-,H CH(CN) 13 3 0.18(O.25),0.27(5) 8.0(0.05) (0.15) 165 PdCl- [P(C H ],,C,,H ONa C H COCH,NO 9

0.11(0.16),0.19(1.6) 2.6g(0.016) (0.1) 166 Pd[P(C H,,) C H,,ONa NO CH(CH -,)NO 13 0.29(O.25), 0.29(2.5) 5.3(0.05) (0.15) 167 PdC1 [P(C H CH ONa NC-CH,NO 13 168. PdCi2[P(C6 5)3]8 oemoNa o 26 0.21(0.29), 0. 34(2. 9) II (0. 3))

TABLE 9 Reaction Ex. time Products g No. hr A (boiling point,n,,B (boiling pointm 158 5.1 g

11 l-2 C/4mm Hg;l.4652 159 15 3.2 6.8 g

122-5/0.05 1657C/0.05mmHg 160 1 8.9 2.3

Product: A: X-CZ-Y X(I Y v CH,CH=CH(CH1)1CH=CH;

(wherein X, Y and Z are as shown in the Table 9) Example 169 In a ml. autoclave were charged 6.7 g. (0.05 mol) of ethyl nitroacetate (NO CH COOC H 0.18 g. (0.25 m. mol) of PdCl [P(C H 0.29 g. (2.5 m. mols) of sodium phenoxide, 15 ml. of benzene and 13 ml. (0.15 mol) of liquefied 1.3- butadiene followed by stirring for 10 hours at 85 C. After removing unreacted materials and benzene by distillation. the residue was distilled under reduced pressure to provide 5.2 g. of ethyl 2-nitro-4,9-decadienoate [CH CH(CH CH CHCH CH(NO )COOC H (having a boiling point of 1l0-l 12 C./ 2 mm. Hg. n,, of 1.4619), 6.1 g. of ethyl 2- nitro-2-(2,7-octadienyl)-4,9-decadienoate (having a boiling point of 154l56 C./ 2 mm. Hg. n,, of 1.4820).

EXAMPLES 170-179 The same procedure as above was repeated while using 0.25 m. mol of palladium or platinum compounds under the same conditions as in Example 169 instead of PdCl [P(C H;,) the results of which are shown in Table 10.

TABLE 10 Products (m) Palladium or platinum e V 7 Example N0, compounds 170 P(I[I(Cgll5)1] 7. '1 1.3 171.... Pd(1rC II5)z 2.3 1.3

ldClz i I 173.. ldlll'zllfllglhh]; 8.1 2.3 17 1.. PtKN n): 1.8 11.8

ll Pdlmcinmh I 176.. PtCl [P(CaH5)3]2 3. 4 2.1 177.. PtIPHCgUQg]; 4. 2 0. 3 178.. Pl.[P(OCsll5)ri]4 3. 6 1.1) 171) PLCzlP(C5lI5)3]g Z. 3 2. 4

EXAMPLE In a 100 ml. autoclave the air in which had been replaced with argon gas were charged 5.7 g. (0.05 mol) of ethyl cyananoacetate, 0.18 g. (0.25 m. mols) of PdCl [P(C H,,) 0.29 g. (2.5 m. mols) of sodium phenoxide, 15 ml. of benzene and 10.2 g. (0. 15 mol) of isoprene followed by stirring for 15 hours for 85 C. After removing unreacted materials and benzene by distillation, the residue was distilled under reduced pressure to provide 5.8 g. of ethyl 2-cyan-4,9- dimethyl-4,9-decadienoate [CH C(CH )(CH CH C(CH )CH CH(CN)COOC H (having a boiling point of from l25l27 C./ 2 mm. Hg.) and 8.2 g. of ethyl 2-cyan-2- (2,7-dimethyl-2,7-octadienyl )-4. 9-dimethyl-4.9-decadienoate [CH C(CH3)(CH CH C(CH CH C(CN)COOC H (having a boiling point of 172l 74 C./ 2 mm. Hg).

EXAMPLE 18 l The same procedure as in Example 180 was repeated while using 0.29 g. (0.25 mol) of Pd [P(C H instead of PdCl [P(C H) to provide 4.8 g. of ethyl 2-cyan-4, 9-dimethyl- 4,9-decadienoate and 9.4 g. of ethyl 2-cyan-2-(2,7-dimethyl- 2,7-octadienyl)-4,9-dimethyl-4,9-decadienoate.

EXAMPLE 182 In a 100 ml. autoclave the air in which had been replaced with argon gas were charged 6.6 g. (0.1 mol) of malononitrile, 0.29 g. (0.25 m. mols) ofPd[P(C,,H 0.29 g. (2.5 m. mols) of sodium phenoxide, 20.4 g. (0.3 mol) of isoprene and 15 ml.

of benzene followed by stirring for 5 hours at 85 C. The reaction liquid thus obtained and benzene were distilled under EXAMPLE 183 EXAMPLE 184 In a 100 ml. autoclave were charged 14.8 g. (0.05 mol) of CGH5SOZCHZSOZCHH5, m. mol) Of H 1 0.58 g. (5 m. mols) of C.,H.-,ONa and 13 ml. (0.15 mol) of liquefied 1,3-butadiene followed by stirring for 20 hours at l20130 C. After removing benzene by distillation, the product was purified by a column chromatography to provide 5.4 g. of (C H SO CHCH CH CHCH CH CH CH CH (having a boiling point of l07109 C./ 10 mm. Hg).

EXAMPLE 185 In a 100 ml. autoclave were charged 9.0 g. (0.05 mol) of C H SOCH CN, 0.35 g. (0.5 m. mol) of PdCl [P(C H 0.27 g. (5 m. mol) of CH ONa, ml. of toluene and 13 ml. (0.15 mol) of liquefied 1,3-butadiene followed by stirring for 10 hours at l40-150 C. After removing toluene by distillation, the product was purified by column chromatography to provide 4.3 g. of C H SO -CH(CN)CH CH CHCH ZCHZCHzbCH EXAMPLE 186 In a 100 ml. autoclave were charged 11.4 g. (0.05 mol) of C6H5SO2CH2COOC2H5, m. mol) of H9 1 0.29 g. (2.5 m. mols) of C.;H ,ONa, 15 ml. ofbenzene and 13 ml. (0.15 mol) of liquefied 1,3-butadiene followed by stirring for hours at 85 C. After removing benzene by I distillation, the product was distilled under reduced pressure to provide 15.8 g. of C H SO CH(COOC H CH CH CHCH CH CH CH CH (having a boiling point of l56l57 C./ 10" mm. Hg, n of 1.5176).

EXAMPLES 187-234 The same procedure as in Example 186 was repeated while using 0.25 m. mol of palladium shown in the following table instead of PdCl [P(C.,H the results of which are shown in Table 11.

TABLE 1 1 Ex. Palladium No. Compounds Products (g) CoHsSOz CH-CHzCH=CH(CHz)3CH=CI-Iz 187 micl 10.4 196 PdCl [P 207 1d[l(CslI5);]1 l1 CCOOClI.-, l5. 8

lIG-COOCI]: 208 PdCl [P(OCHH.S)I\]2 EXAMPLE 235 in a ml. autoclave were charged 1 1.4 g. (0.05 mol) o1- C.,H SOCH COOC H 0.35 g. (0.5 m. mol) of PdCl [P(C,; H a[ 0.58 g. (5 m. mol) ofC.,H,,ONa, and 15 ml. of benzene The air in the autoclave was replaced with an argon gas, then charged with 10.2 g. (0.15 mol) of isoprcne followed by stirring for 20 hours at 130 C. After removing benzene, the reaction liquid this obtained was distilled under reduced pressure to provide 15.8 g. of C,,H -;SO CH(COOC-,H )CH C(CH CHCH CH C(CH,,)CH CH (having a boiling point of l74l 76 C./ 10 mm. Hg).

EXAMPLE 236 in a 100 ml. autoclave were charged 6.0 g. (0.034 mol) n- C H SO CH CONH 0.35 g. 0.5 m. mol) of [PdCl P(C ,H 0.85 g. (5 m. mol) of C H ONa, 15 ml. of toluene and 10 ml (0.1 mol) of liquefied 1,3-butadiene followed by stirring for 20 hours at -150 C. After removing toluene by distil lation, the residue was distilled under reduced pressure to provide 6.9 g. of n-C H,,SO CH(CONH )CH CH CHCH CH CH CH (having a boiling point of l99-20 0 C./10' mm. Hg., and a melting point of 8789 C.), 1.8 g. of nC H SO C(CONH (CH CH CHCH CH CH CH CH (having a boiling point of 227-230 C./ 10 mm. Hg, melting point of 9698 C.

EXAMPLE 237 In a 100 ml. autoclave were charged 9.3 g. (0.05 mol) of C H SOCH CONH 0.35 g. (0.5 m. mol) of PdCl [P(C H 0.58 g. of C H ONa, 30 m1. of acetone and 13 mol. (0.15 mol) of liquefied 1,3-butadiene followed by stirring for 20 hours at 120l 30 C. After removing acetone, by distillation, the product was distilled under reduced pressure to provide 13.2 g. of C H SO CH(CONH )CH CH CH(CH CH CH, (having a boiling point of from 200 to 204 C./10"" mm. Hg).

EXAMPLE 238 The same procedure as above was repeated while using 10 g. (0.05 mol) of p-CH -C H SO CH CONH instead of C H SOCH CONH to provide 10.8 g. of p--CH C H SO C H(CONH )CH CH CHCH CH CH CH CH (having a boiling point offrom 213 to 216 C./l0"" mm. Hg.

We claim:

1. A process for the preparation of 1,6-octadiene derivatives by the reaction between a compound represented by the general formula X--CH(Z)Y wherein X and Y each represent a member selected from the group consisting of CHO, COR, CO R and, CON(R"") and, wherein R, R and R each represents a monovalent hydrocarbon radical selected from the group consisting of an aliphatic group having from one to 10 carbon atoms, an alicyclic group having from six to 10 carbon atoms and an aromatic group having from six to 10 carbon atoms, R"" represents a member selected from the group consisting of a hydrogen atom and a monovalent hydrocarbon radical as defined above, and R may be an alkylene group having from two to 10 carbon atoms bonded to 2, when X or Y is COR and Z represents a member selected from the group consisting of a hydrogen atom, an alkyl group having from one to eight carbon atoms, a cycloalkyl group having from six to eight carbon atoms and an aryl group having from six to eight carbon atoms, and 2 may be an alkylene group having from two to 10 carbon atoms bonded to X or Y when X or Y is COR, and a 1,3-diene compound represented by the general formula R1 R2 R3 CH1=CC:CH

wherein R R and R each represent a member selected from the group consisting of a hydrogen atom and an alkyl group having from one to six carbon atoms, in the presence of a palladium catalyst or platinum catalyst at a temperature of from to 250 C, said platinum or palladium catalyst being selected from the group consisting of a. platinum or palladium inorganic salts,

b. platinum or palladium organic salts,

c, platinum or palladium complex compounds with trivalent phosphorus, arsenic and antimony compounds,

d, platinum or palladium complex compounds with organic ligands,

e. platinum or palladium complex compounds with ammonium compounds, and

f. platinum or palladium complex compounds with nitrogencontaining ligands.

2. A process according to claim 1 where a compound selected from the group consisting of alkali metals and basic alkali metal salts is used as cocatalyst together with a palladium catalyst or a platinum catalyst.

3. A process according to claim 1 where the reaction is can ried out in the presence of a phenol.

4. A process according to claim 1 where the l,3-diene compound is one selected from the group consisting of l,3-butadiene, isoprene, 2,3-di-methylbutadiene, and 1,3-pentadiene.

5. A process for the preparation of l,6-octadiene derivatives by the reaction between a compound represented by the general formula X-CH(Z)Y wherein X and Y each represent a member selected from the group consisting of COR and CO R", wherein R and R" each represents a monovalent hydrocarbon radical selected from the group consisting of an aliphatic group having from one to carbon atoms, an alicyclic group having from six to I0 carbon atoms, and an aromatic group having from six to 10 carbon atoms, and R may be an alkylene group having from two to 10 carbon atoms bonded to Z, when X or Y is COR and 2 represents a member selected from the group consisting of a hydrogen atom, an alkyl group having from one to eight carbon atoms, a cycloalkyl group having from six to eight carbon atoms and an aryl group having from six to eight carbon atoms, and Z may be an alkylene group having from two to ID carbon atoms bonded to X or Y when X or Y is COR, and a 1,3-diene compound represented by the general formula 1 R2 R1 CII2=JJ( J:t 3H

wherein R R and R each represent a member selected from the group consisting of a hydrogen atom and an alkyl group having from one to six carbon atoms, in the presence ofa palladium catalyst or platinum catalyst at a temperature of from 0 to 250 C., said platinum or palladium catalyst being selected from the group consisting of a. platinum or palladium inorganic salts,

b. platinum or palladium organic salts,

c. platinum or palladium complex compounds with trivalent phosphorus, arsenic and antimony compounds,

d. platinum or palladium complex compounds with organic ligands,

e. platinum or palladium complex compounds with am monium compounds, and

f. platinum or palladium complex compounds with nitrogencontaining ligands.

6. A process according to claim 5, where a compound selected from the group consisting of alkali metals and basic alkali metal salts is used as cocatalyst together with a palladium catalyst or a platinum catalyst.

7. A process according to claim 5, where the reaction is carried out in the presence ofa phenol.

8. A process according to claim 5, where the 1,3-diene compound is one selected from the group consisting of 1,3-butadiene, isoprene, 2,3-di-methylbutadiene, and l,3-pentadiene. 

2. A process according to claim 1 where a compound selected from the group consisting of alkali metals and basic alkali metal salts is used as cocatalyst together with a palladium catalyst or a platinum catalyst.
 3. A process according to claim 1 where the reaction is carried out in the presence of a phenol.
 4. A process according to claim 1 where the 1,3-diene compound is one selected from the group consisting of 1,3-butadiene, isoprene, 2,3-di-methylbutadiene, and 1,3-pentadiene.
 5. A process for the preparation of 1,6-octadiene derivatives by the reaction between a compound represented by the general formula X-CH(Z)-Y wherein X and Y each represent a member selected from the group consisting of COR'' and CO2R'''', wherein R'' and R'''' each represents a monovalent hydrocarbon radical selected from the group consisting of an aliphatic group having from one to 10 carbon atoms, an alicyclic group having from six to 10 carbon atoms, and an aromatic group having from six to 10 carbon atoms, and R'' may be an alkylene group having from two to 10 carbon atoms bonded to Z, when X or Y is COR'' and Z represents a member selected from the group consisting of a hydrogen atom, an alkyl group having from one to eight carbon atoms, a cycloalkyl group having from six to eight carbon atoms and an aryl group having from six to eight carbon atoms, and Z may be an alkylene group having from two to 10 carbon atoms bonded to X or Y when X or Y is COR'', and a 1,3-diene compound represented by the general formula wherein R1, R2 and R3 each represent a member selected from the group consisting of a hydrogen atom and an alkyl group having from one to six carbon atoms, in the presence of a palladium catalyst or platinum catalyst at a temperature of from 0* to 250* C., said platinum or palladium catalyst being selected from the group consisting of a. platinum or palladium inorganic salts, b. platinum or palladium organic salts, c. platinum or palladium complex compounds with trivalent phosphorus, arsenic and antimony compounds, d. platinum or palladium complex compounds with organic ligands, e. platinum or palladium complex compounds with ammonium compounds, and f. platinum or palladium complex compounds with nitrogen-containing ligands.
 6. A process according to claim 5, where a compound selected from the group consisting of alkali metals and basic alkali metal salts is used as cocatalyst together with a palladium catalyst or a platinum catalyst.
 7. A process according to claim 5, where the reaction is carried out in the presence of a phenol.
 8. A process according to claim 5, where the 1,3-diene compound is one selected from the group consisting of 1,3-butadiene, isoprene, 2,3-di-methylbutadiene, and 1,3-pentadiene. 